Dyestuffs of the anthraquinone series



Patented Jan. 30, 1940 UNITED?" STATES PATENT F-Fiilli? 2,188,776 DYESTUFVFS OF THE ANTHRAQUINONE seams Ralph N. Lulek, Milwaukee, Wis.',assignor.to E. I. du Iont deNemours & Company, Wilmington,- DeL, a corporation of Delaware No Drawing-"'Application April 14, 1938, I I

. seriar-No. 201935 zolaim'a- (c1. zoo-e16);-

This inyention relates to the" preseason or a series; more-"particularly tomercenaries of a dyestufiof the anthriniidecarbazoleQtype'which 5 -dyes cotton in desirable dark red-brown shades and which-will pdssess the good fastness properties of that class of dyestuffs.

In Example 8 of German Patent 566,708 there is described the preparation of a dyestuff by the brown range must be suitable for mixing with known colors to give these desirable shades, attempts have been made to produce a dark brown dyestuil in this same class. I It is therefore an object of this invention to produce a brown dyestuif of the series commonly known as the anthrimidecarbazoles which will dye cotton in deep red brown shades, and which v) is suitable as a self-dyeing color and for use in mixtures with known colors to give dark maroon and dark brown shades. s I I have found that by altering the conditions m under which the 414"-dibenzoylamino-l',l",1,5-

' trianthrimide of the formula:

0:5, ss e? $3 a is ring-closed with aluminum chloride a new and valuable dark red-brown .dyestuff can be pro- 60 duced which is particularly suitable for use in,

the preparation of "mixtures to give maroon and deep dark brown dyestuffs.

am-i notria nthrimide ';is carried out under more mild conditions than those disclosed for the" preparation of the' coloir in Example '8 of German Patent 566,708. By tore mild conditions I mean the use of less aluminum chloride and/or lowerv temperatures. The reaction is preferably carried out without isolation of the intermediate anthrimide from the nitrcbenzene solution in which the anthrimlde is formed. The trianthrimide is prepared by the condensation of two molecular parts of 1-benzoyla1nino-4-chloroanthraquinone with one molecular part of 1,5-diaminoanthraquinone in nitro'benzene and in the presence of' an acid binding agent and a copper catalyst. When the ring-closure is carried out in the same nitrobenzene solution in which the anthrimide is formed, from 2%, to k /2 parts of aluminum chloride, based on the trianthrirnide compound, should be used. With this range in such as 42/ parts, are employed the temperature should not be above 65 to 80 C. If only 21/ parts of aluminum chloride are'used the temperature should be maintained between 95 and 100 C. .With intermediate amounts of aluminum chloride, the intermediate temperatures should be used, The difference in color of the dyestuff obtained by this modified'reaction over that obtained by the process of Example 8 or German Patent 566,708 is entirely unexpected and could H 7' This newdyestuif is obtained when the'ring closure of the dibenzoyl not be predicted from any disclosure found in j that patent or in the prior art known to applicant.

The following example is given to illustrate a preferred process by which this color may be produced.

Example mass is then cooled to room temperature and 960 parts aluminum chloride are added in portions over a period of one hour, permitting the term perature to rise to 60 C. When the addition of the aluminum chloride is completed the charge is heated to 90 Cpand held at this temperature for one hour. After cooling to room temperature the charge is drowned in ice water and the nitrobenzene removed by steam distillation.

The dyestuff is filtered, washed, and dried. It may be converted into a pasteby dissolving in dark red vat in bluish dark brown shades of excellent fast'ness properties, said dyestufi being substantially identical in color with the dyestuff v obtained by the aluminum chloride ring-closure of the 4:,4"-dibenzoylamino-l,l': 5,1"-trianthrimide in nitrobenzene, at a temperature of 90 C., with 3 parts of aluminum chloride per part of trianthrimide, said dyestuii being obtained by the aluminum chloride ring-closure of 42 4"-dibenzoylamino-1,1: 5,l"-trianthrimide in nitrobenzene, the amount of aluminum chloride being within the range of from 2% to 4 parts per part of trianthrimide and the reaction being carried out attemperatures within the rangeof from 65 to 100 C.

2. The process for preparing a new bluish dark brown. vat dyestufi of the anthrimidecarbazole type which comprises reacting the 4',4" dibenzoylamino-1,1': 5,1" triarithrimide with aluminum chloride in nitrobenzene' under conditions sufficiently mild to give a .dyestufivof substantially the same color as that dye obtained 7 by heating i541"-dibenzoylamino-l,1: 5,1trianthrimide in nitro benzene at a temperature of. 90 C. with 3 parts of aluminum chlorideiper part of trianthrimide, the amount of aluminum chloride employed being within the range of 2 to 4 parts per part of anthrimide contained in the reaction mass and the temperature of fusion being between 65 and'100 C. 1

. 20 RALPH N. LULEK. 

